Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes

Weber L, Werner V, Fox MA, Marder TB, Schwedler S, Brockhinke A, Stammler H-G, Neumann B (2009)
Journal of the Chemical Society. Dalton Transactions (8): 1339-1351.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
A series of π-conjugated systems with two and three 1,3-diethyl-1,3,2-benzodiazaborolyl end-groups was synthesised in 58-91% yields using established 1,3,2-diazaborole methodologies. The bis(diazaborolyl) compounds contain thiophene -2,5-C4H2S- (2a), dithiophene -5,5'-(2,2'-C4H2S)(2)- (2b), phenylene -1,4-C6H4- (2c), biphenylene - 4,4'-(1,1'-(C6H4)(2))- (2d) and dioctylfluorene -2,7-(9,9-(C8H7)(2)C11H6)- (2e) bridges. The three-way linkers in the tris(diazaborolyl) assemblies contain a central phenylene unit - 1,3,5-C6H3- linked to the borolyl end groups via thiophene - 2,5-C4H2S- (3a), directly bonded (3b) or via phenylene - 1,4-C6H4- (3c) units. Molecular structures of 2a, 2b, 2c, 3a, 3b and 3c were determined by X-ray crystallographic studies. These borolylated systems show intense blue/violet luminescence with Stokes shifts of 6200-9500 cm(-1) and quantum yields of 0.33 to 0.98. The absorption maxima (296-351 nm) of these assemblies are reproduced well by TD-DFT computations (B3LYP/6-31G*), and arise from strong, low energy HOMO-LUMO transitions. From molecular orbital computations on optimised geometries of these diazaborolyl systems, the LUMO is located mainly on the thiophene/benzene bridge (66-92%) while the HOMO is largely benzodiazaborolyl in character (53-83%). The S-1 <- S-0 absorption bands are thus assigned to π(diazaborolyl)-π*(thiophene/benzene) transitions. Computations on related bis(boryl) dithiophenes [ with diarylboryl e. g. Ph2B, Mes(2)B, (C6F5)(2)B and FMes(2)B (Mes = 2,4,6-Me3C6H2; FMes = 2,4,6-(CF3)(3)C6H2), dioxaborolyl and other diazaborolyl groups] reveal strong, low energy UV-visible absorption bands arising from π(thiophene)-π*(thiophene) transitions, with increasing boron participation in the LUMO of the diarylboryl and especially the highly fluorinated systems.
Erscheinungsjahr
Zeitschriftentitel
Journal of the Chemical Society. Dalton Transactions
Ausgabe
8
Seite(n)
1339-1351
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eISSN
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Weber L, Werner V, Fox MA, et al. Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions. 2009;(8):1339-1351.
Weber, L., Werner, V., Fox, M. A., Marder, T. B., Schwedler, S., Brockhinke, A., Stammler, H. - G., et al. (2009). Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions(8), 1339-1351. doi:10.1039/b815931a
Weber, L., Werner, V., Fox, M. A., Marder, T. B., Schwedler, S., Brockhinke, A., Stammler, H. - G., and Neumann, B. (2009). Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions, 1339-1351.
Weber, L., et al., 2009. Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions, (8), p 1339-1351.
L. Weber, et al., “Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes”, Journal of the Chemical Society. Dalton Transactions, 2009, pp. 1339-1351.
Weber, L., Werner, V., Fox, M.A., Marder, T.B., Schwedler, S., Brockhinke, A., Stammler, H.-G., Neumann, B.: Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions. 1339-1351 (2009).
Weber, Lothar, Werner, Vanessa, Fox, Mark A., Marder, Todd B., Schwedler, Stefanie, Brockhinke, Andreas, Stammler, Hans-Georg, and Neumann, Beate. “Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes”. Journal of the Chemical Society. Dalton Transactions 8 (2009): 1339-1351.

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PMID: 29543358
Pyrene Molecular Orbital Shuffle-Controlling Excited State and Redox Properties by Changing the Nature of the Frontier Orbitals.
Merz J, Fink J, Friedrich A, Krummenacher I, Al Mamari HH, Lorenzen S, Haehnel M, Eichhorn A, Moos M, Holzapfel M, Braunschweig H, Lambert C, Steffen A, Ji L, Marder TB., Chemistry 23(53), 2017
PMID: 28718975
Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2-Diazaboroles.
Su B, Li Y, Ganguly R, Kinjo R., Angew Chem Int Ed Engl 56(46), 2017
PMID: 28906070
Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups.
Zhang Z, Edkins RM, Edkins RM, Nitsch J, Fucke K, Steffen A, Longobardi LE, Stephan DW, Lambert C, Marder TB., Chem Sci 6(1), 2015
PMID: 28966759
A planarized triphenylborane mesogen: discotic liquid crystals with ambipolar charge-carrier transport properties.
Kushida T, Shuto A, Yoshio M, Kato T, Yamaguchi S., Angew Chem Int Ed Engl 54(23), 2015
PMID: 25907576
Highly electron-deficient and air-stable conjugated thienylboranes.
Yin X, Chen J, Lalancette RA, Marder TB, Jäkle F., Angew Chem Int Ed Engl 53(37), 2014
PMID: 25044554
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PMID: 25089659
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PMID: 23403937
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57 References

Daten bereitgestellt von Europe PubMed Central.


Entwistle, Angew. Chem., Int. Ed. 41(), 2002

Entwistle, Chem. Mater. 16(), 2004

Elbing, Angew. Chem., Int. Ed. 47(), 2008

Weber, Coord. Chem. Rev. 252(), 2008

Weber, Eur. J. Inorg. Chem. (), 2006

Weber, Organometallics 19(), 2000
Chemistry. Boron goes on the attack.
Marder TB., Science 314(5796), 2006
PMID: 17023642
Boryllithium: isolation, characterization, and reactivity as a boryl anion.
Segawa Y, Yamashita M, Nozaki K., Science 314(5796), 2006
PMID: 17023656
Ruthenium-catalyzed regiospecific borylation of methyl C-H bonds.
Murphy JM, Lawrence JD, Kawamura K, Incarvito C, Hartwig JF., J. Am. Chem. Soc. 128(42), 2006
PMID: 17044685

Weber, Organometallics 20(), 2001

Suginome, Angew. Chem., Int. Ed. 44(), 2005

Weber, Organometallics 24(), 2005

Maruyama, J. Mater. Chem. 12(), 2002

Weber, Dalton Trans. (), 2006

Weber, Dalton Trans. (), 2006

Weber, Z. Anorg. Allg. Chem. 633(), 2007

Weber, Z. Anorg. Allg. Chem. 627(), 2001

Mueller-Westerhoff, Tetrahedron 47(), 1991

Raeder, J. Org. Chem. 6(), 1941

Kohler, Z. Naturforsch. B: Chem. Sci. 57(), 2002
Electronic communication and negative binding cooperativity in diborylated bithiophenes.
Sundararaman A, Venkatasubbaiah K, Victor M, Zakharov LN, Rheingold AL, Jakle F., J. Am. Chem. Soc. 128(51), 2006
PMID: 17177405

Cao, J. Organomet. Chem. 689(), 2004
Self-assembling poly(dioxaborole)s as blue-emissive materials.
Niu W, Smith MD, Lavigne JJ., J. Am. Chem. Soc. 128(51), 2006
PMID: 17177372

Rodríguez-Cuamatzi, Acta Crystallogr. E60(), 2004

Rodríguez-Cuamatzi, Angew. Chem., Int. Ed. 43(), 2004

Niu, Chem. Commun. (), 2005

Haberecht, Z. Anorg. Allg. Chem. 630(), 2004

Rodriguez, Angew. Chem., Int. Ed. 43(), 2004

Yuan, Appl. Organomet. Chem. 10(), 1996

Tong, Chem. Commun. (), 2006

Okada, J. Chem. Soc., Chem. Commun. (), 1992

Kinoshita, Chem. Lett. (), 2001

Habereder, Appl. Organomet. Chem. 17(), 2003

Noda, Adv. Mater. 11(), 1999

Siddle, New J. Chem. 31(), 2007
Acceptor or donor (diaryl B or N) substituted octupolar truxene: synthesis, structure, and charge-transfer-enhanced fluorescence.
Yuan MS, Fang Q, Liu ZQ, Guo JP, Chen HY, Yu WT, Xue G, Liu DS., J. Org. Chem. 71(20), 2006
PMID: 16995698

Cao, J. Mol. Struct. 874(), 2008

Zhou, Adv. Funct. Mater. 18(), 2008

Yuan, Chem.–Eur. J. 12(), 2006

Porrès, Proc. SPIE 5934(), 2005

Entwistle, Chem. Commun. (), 2004

Entwistle, J. Organomet. Chem. 680(), 2003

Yuan, J. Solid State Chem. 154(), 2000

Yuan, J. Organomet. Chem. 449(), 1993

Yuan, J. Chem. Soc., Chem. Commun. (), 1990

Weber, Eur. J. Inorg. Chem. (), 2006

Shirota, J. Mater. Chem. 10(), 2000

Cornet, Dalton Trans. (), 2003

Plater, J. Chem. Soc., Perkin Trans. 1 (), 2000

Zhu, Acta Crystallogr. E62(), 2006

Sheldrick, Acta Crystallogr., Sect. A 64(), 2008

Becke, J. Chem. Phys. 98(), 1993
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.
Lee C, Yang W, Parr RG., Phys. Rev., B Condens. Matter 37(2), 1988
PMID: 9944570

Petersson, J. Chem. Phys. 94(), 1991

Petersson, J. Chem. Phys. 89(), 1988

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